UPLC-Orbitrap-MS/MS combined with chemometrics establishes variations in chemical components in green tea from Yunnan and Hunan origins.

Multi-components of green tea from different origins were identified by UPLC-Orbitrap-MS/MS, including alkaloids, amino acids, catechins, flavones, flavone glycosides, phenolic acids and theaflavins. Quantitative chemical profiles of 72 samples of Yunnan green tea (YGT) and Hunan green tea (HGT) established the influence of origin on green tea. In addition, three variable selection methods, based on partial least squares-discriminant analysis (PLS-DA), were employed to screen characteristic components of YGT and HGT. The results of variable importance on projection (VIP) method showed better performance than coefficients β and the least absolute shrinkage and selection operator (LASSO) for this dataset. Three characteristic components, named, gallocatechin gallate (GCG), epicatechin-(4β → 8)-epigallocatechin-3-O-gallate, and vitexin were selected by VIP, with a correct rate of 98.61% and an AUC value of 0.9706. The results indicated that the combination of UPLC-Orbitrap-MS/MS and chemometrics could serve as a valid strategy to analyze complex analytical objects, such as green tea.

[1]  Peter Bühlmann.  Regression shrinkage and selection via the Lasso: a retrospective (Robert Tibshirani): Comments on the presentation , 2011 .

[2]  Jun-feng Tan,et al.  Study of the dynamic changes in the non-volatile chemical constituents of black tea during fermentation processing by a non-targeted metabolomics approach , 2016 .

[3]  L. Bazinet,et al.  Rapid HPLC-MS method for the simultaneous determination of tea catechins and folates. , 2014, Journal of agricultural and food chemistry.

[4]  Xiaoye He,et al.  Chemical fingerprint analysis for quality control and identification of Ziyang green tea by HPLC. , 2015, Food chemistry.

[5]  Qi Chen,et al.  Identification of green tea origins by near-infrared (NIR) spectroscopy and different regression tools , 2017 .

[6]  Eun-hee Kim,et al.  Metabolomic unveiling of a diverse range of green tea (Camellia sinensis) metabolites dependent on geography. , 2015, Food chemistry.

[7]  Matej Oresic,et al.  MZmine 2: Modular framework for processing, visualizing, and analyzing mass spectrometry-based molecular profile data , 2010, BMC Bioinformatics.

[8]  K. Suk,et al.  Anti-inflammatory effects of catechols in lipopolysaccharide-stimulated microglia cells: inhibition of microglial neurotoxicity. , 2008, European journal of pharmacology.

[9]  Jianbo Xiao.  Phytochemicals in medicine and food , 2015, Phytochemistry Reviews.

[10]  Lunzhao Yi,et al.  Metabolomic identification of novel biomarkers of nasopharyngeal carcinoma , 2014 .

[11]  Karl Fraser,et al.  Analysis of metabolic markers of tea origin by UHPLC and high resolution mass spectrometry , 2013 .

[12]  E. Çapanoğlu,et al.  Advance on the Flavonoid C-glycosides and Health Benefits , 2016, Critical reviews in food science and nutrition.

[13]  R. Brereton,et al.  Partial least squares discriminant analysis: taking the magic away , 2014 .

[14]  Hong Wang,et al.  Cancer Preventive Activities of Tea Catechins , 2016, Molecules.

[15]  S. Agarwal,et al.  Antiobesity effects of green tea catechins: a mechanistic review. , 2011, The Journal of nutritional biochemistry.

[16]  Yizeng Liang,et al.  Chemometric methods in data processing of mass spectrometry-based metabolomics: A review. , 2016, Analytica chimica acta.

[17]  Lunzhao Yi,et al.  Chemical features of Pericarpium Citri Reticulatae and Pericarpium Citri Reticulatae Viride revealed by GC-MS metabolomics analysis. , 2015, Food chemistry.

[18]  K. Li,et al.  Simultaneous determination of theanine, gallic acid, purine alkaloids, catechins, and theaflavins in black tea using HPLC. , 2010 .

[19]  Chi-Tang Ho,et al.  Stability of tea polyphenol (-)-epigallocatechin-3-gallate and formation of dimers and epimers under common experimental conditions. , 2005, Journal of agricultural and food chemistry.

[20]  Yi-Tao Wang,et al.  Simultaneous determination of caffeine, gallic acid, theanine, (−)-epigallocatechin and (−)-epigallocatechin-3-gallate in green tea using quantitative 1H-NMR spectroscopy , 2014 .

[21]  Yizeng Liang,et al.  An ultra high performance liquid chromatography with tandem mass spectrometry method for plasma and cerebrospinal fluid pharmacokinetics of rhein in patients with traumatic brain injury after administration of rhubarb decoction. , 2015, Journal of separation science.

[22]  Victoria Samanidou,et al.  Simultaneous determination of polyphenols and major purine alkaloids in Greek Sideritis species, herbal extracts, green tea, black tea, and coffee by high-performance liquid chromatography-diode array detection. , 2012, Journal of separation science.

[23]  Brian Everitt,et al.  Cluster analysis , 1974 .

[24]  Lunzhao Yi,et al.  Comprehensive characterization and identification of antioxidants in Folium Artemisiae Argyi using high-resolution tandem mass spectrometry. , 2017, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[25]  H. Kelebek.  LC-DAD-ESI-MS/MS characterization of phenolic constituents in Turkish black tea: Effect of infusion time and temperature. , 2016, Food chemistry.

[26]  Lunzhao Yi,et al.  GC-MS Fingerprinting Combined with Chemometric Methods Reveals Key Bioactive Components in Acori Tatarinowii Rhizoma , 2017, International journal of molecular sciences.

[27]  Dong-Sheng Cao,et al.  A new strategy to prevent over-fitting in partial least squares models based on model population analysis. , 2015, Analytica chimica acta.

[28]  Chae-Wook Kim,et al.  GCG-Rich Tea Catechins are Effective in Lowering Cholesterol and Triglyceride Concentrations in Hyperlipidemic Rats , 2008, Lipids.

[29]  Yizeng Liang,et al.  Prediction of peptide fragment ion mass spectra by data mining techniques. , 2014, Analytical chemistry.

[30]  A. Maćkiewicz,et al.  Principal Components Analysis (PCA) , 1993 .

[31]  D. Kwon,et al.  Antibacterial activity of epigallocatechin-3-gallate (EGCG) and its synergism with β-lactam antibiotics sensitizing carbapenem-associated multidrug resistant clinical isolates of Acinetobacter baumannii. , 2017, Phytomedicine : international journal of phytotherapy and phytopharmacology.

[32]  Zhiguang Zhou,et al.  Simultaneous determination of eight catechins and four theaflavins in green, black and oolong tea using new HPLC-MS-MS method. , 2016, Journal of pharmaceutical and biomedical analysis.

[33]  D. Everett,et al.  Antioxidant activity and recovery of green tea catechins in full-fat cheese following gastrointestinal simulated digestion , 2016 .

[34]  P. Plaza-Bolaños,et al.  Identification and quantification of phytochemicals in nutraceutical products from green tea by UHPLC-Orbitrap-MS. , 2015, Food chemistry.

[35]  Yaping Guo,et al.  Epimerization of epigallocatechin gallate to gallocatechin gallate and its anti-diabetic activity , 2013, Medicinal Chemistry Research.

[36]  Tahir Mehmood,et al.  A review of variable selection methods in Partial Least Squares Regression , 2012 .

[37]  G. Fu,et al.  Stable biomarker screening and classification by subsampling-based sparse regularization coupled with support vector machines in metabolomics , 2017 .

[38]  A. Sugimoto,et al.  Heat-epimerized tea catechins rich in gallocatechin gallate and catechin gallate are more effective to inhibit cholesterol absorption than tea catechins rich in epigallocatechin gallate and epicatechin gallate. , 2003, Journal of agricultural and food chemistry.

[39]  Kuan Hu,et al.  Qualitative and quantitative evaluation of Microctis Folium (the leaves of Microcos paniculata L.) by high performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry , 2014 .